JP4847972B2 - Water repellent for glass - Google Patents

Description

The present invention is a water-repellent treatment agent that imparts water repellency to automobile window glass, architectural window glass, and other glass. The present invention relates to a simple water-repellent treatment agent that has an immediate effect after being applied to the vehicle. Specifically, the water-repellent treatment agent can be used as a wind washer that is loaded into a vehicle body such as an automobile and ejected from a nozzle. It is.

Conventionally, amino-modified polysiloxane (so-called aminosilicone) is changed to unmodified polysiloxane for the purpose of manufacturing a water-repellent agent for glass that can be used even when moisture remains on the glass surface and is easy to handle and safe. Have been developed.

Furthermore,
(1) While improving the water solubility of amino-modified polysiloxane,
(2) When the amino-modified polysiloxane has an alkoxy group, the crosslinking of the alkoxy groups is catalyzed or the reaction between the alkoxy group and the SiOH group on the glass surface is catalyzed. For the purpose of increasing the adsorptivity to the glass surface, a method using an acid has been developed. Among them, a weak acid such as formic acid or lactic acid is used in combination with an amino-modified polysiloxane instead of an acid that is dangerous to handle. Have been developed (Patent Document 1, Patent Document 2, etc.).

However, these water-repellent treatment agents containing aminosilicones are excellent in water repellency immediately after application, but have poor sustainability. For example, when they are rained after application, they are several tens of times. There was a tendency for the effect to be lost in seconds.

On the other hand, in order to improve water repellency, a technology that uses other silicones in combination with aminosilicones has been proposed for defrosting and deicing agents (Patent Document 3).

This defrosting deicing agent is intended to provide water repellency with water-insoluble silicone so that the melted ice does not refreeze at the same time as the defrosting, It is intended to improve the “initial water repellency” after application by hydrophobizing the water after deicing with water-insoluble silicone and preventing adhesion to the glass surface. It does not solve the above-mentioned problem that the water-repellent effect does not last.

In addition, when the glass water repellent is a wind washer loaded on the body of an automobile, the temperature of the automobile body, such as temperature control and other difficult quality control conditions, for example, changes from below zero to nearly 60 ° C. Depending on the internal environment of the automobile, the wind washer may be altered and clogged with the nozzle, or when the wind washer is scattered and adsorbed on the painted surface of the car body due to the alcohol component etc. contained, It is desired to solve problems such as changing the color of paint due to differences in the refractive index of light.

JP 7-41336 A JP 10-102046 A JP 2004-59846 A

Accordingly, an object of the present invention is to provide a water repellent for glass that maintains water repellency not only after initial application but also after rain, etc. An object of the present invention is to provide a water repellent for glass that hardly changes in quality even in a harsh environment in an automobile and does not cause discoloration of the painted surface of the vehicle body.

The above object can be achieved by the following first to ninth inventions.

<First invention>
A water-repellent agent for glass comprising an amino-modified polysiloxane, an acid, and an activator, further comprising aminosilane.

<Second invention>
Furthermore, the water repellent for glass according to the first invention, further comprising a water-soluble solvent.

<Third invention>
The water-repellent agent for glass according to the first invention or the second invention, wherein the amino-modified polysiloxane has the following properties (A) and / or (B).
(A) The kinematic viscosity at 25 ° C. is 10 to 5000 cst.
(B) Amino equivalent is 100-15000.

<Fourth Invention>
The water repellent for glass according to any one of the first to third inventions, wherein the aminosilane has 2 to 3 reactive functional groups in addition to the amino group.

<Fifth invention>
Any of the first to fourth inventions characterized in that the content of amino-modified polysiloxane is 0.01 to 10.0% by mass and the content of aminosilane is 0.01 to 1% by mass. The water repellent for glass according to crab.

<Sixth invention>
The water repellent for glass according to any one of the first to fifth inventions, wherein the content ratio of amino-modified polysiloxane and aminosilane is 1: 2 to 10: 1.

<Seventh invention>
The water repellent for glass according to any one of the first to sixth inventions, wherein a neutralization rate is 50 to 10%.

<Eighth invention>
The water repellent for glass according to any one of the first to seventh inventions, wherein the aminosilane includes a compound represented by the following formula [1].

(In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms;
R ³ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
X is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
a is an integer of 0 to 5;
b is an integer of 0-2. )

<Ninth Invention>
A wind washer comprising the water repellent for glass according to any one of the first invention to the eighth invention.

The water repellent for glass of the present invention is a water repellent for glass that maintains water repellency not only after initial application but also after rain.
Further, among the present invention, the specific ones have the effect of being particularly excellent in the effect that they are hardly deteriorated even under a severe environment in the automobile, and the possibility of discoloration of the painted surface of the vehicle body is greatly improved. ing.

[Definition of water repellent for glass]
The water repellent for glass of the present invention imparts water repellency to the glass surface, including not only the product name of water repellent, but also the names of window washer, glass cleaner, defrosting agent, deicing agent and other products. It is intended to include all compositions that have at least one objective.

[Amino-modified polysiloxane used in the present invention]
The amino-modified polysiloxane used in the present invention is a polysiloxane having an amino group at the side chain and / or terminal.

Any amino-modified polysiloxane may be used as long as it is a known one used for water repellents, and various amino groups can be used.

In addition, it is preferable that this amino modified polysiloxane is a C1-C3 alkyl group or a C1-C3 alkoxy group at the terminal.

Alkoxy groups cause hydrolysis in the presence of water, cause a crosslinking reaction, and increase the degree of polymerization, making it difficult to dissolve in water and difficult to be washed away by rain. Alkoxy groups are preferred from the standpoint of reacting with SiOH groups and chemically adsorbing to the glass surface, making them more resistant to rain and wiping and increasing water repellency, while glass water repellency. From the viewpoint that the quality of the agent is kept constant, an alkyl group is more preferable.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and the like. Among them, a methyl group is preferable.
Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group.

The ends of the amino-modified polysiloxane used in the present invention may be the same or different.

Specific examples of the amino-modified polysiloxane include, but are not limited to, those represented by the following formula [2] or [3]. More than one type can be used in combination.

In the above formula [2], X and Y are preferably the above-mentioned alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and among them, a methyl group or an alkoxy group. Wherein l and m are integers of 1 or more, A ¹ is preferably —R ⁵ —NH ₂ or —R ⁶ NHR ⁷ NH ₂ , and R ⁵ , R ⁶ and R ⁷ are each represented by Independently representing a divalent hydrocarbon, the divalent hydrocarbon is, for example, generally a hydrocarbon group having 1 to 5 carbon atoms, specifically, an ethylene group, a propylene group, etc. It is preferable that the amino-modified polysiloxane has a kinematic viscosity at 25 ° C. and an amino equivalent that are suitable values described below.

Specifically, the amino-modified polysiloxane represented by the above formula [2] can be obtained from the market as the following.

In the above formula, A ² and A ³ each independently represent a methyl group, an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), —R ⁸ —NH ₂ , or —R ⁹ NHR ¹⁰ NH ₂ ; At least one is —R ⁸ —NH ₂ or —R ⁹ NHR ¹⁰ NH ₂ . R ⁸ , R ⁹ and R ¹⁰ each independently represents a divalent hydrocarbon group, and n represents an integer of 1 or more.

In the above general formula [3], the divalent hydrocarbon group represented by R ⁸ , R ⁹ and R ¹⁰ is not particularly limited, but is generally a hydrocarbon group having 1 to 5 carbon atoms. Specifically, an ethylene group, a propylene group, etc. are mentioned. In the general formula [3], n is preferably an integer that satisfies the kinematic viscosity and equivalent weight described later.

Specifically, the amino-modified polysiloxane represented by the above formula [3] can be obtained from the market as the following.

The amino-modified polysiloxane used in the present invention preferably has a kinematic viscosity at 25 ° C. of 10 to 5000 cst, more preferably 20 to 1000 cst.

This is because when it is 10 cst or more, it has an advantage that it is particularly difficult to form an oil film at 5000 cst or less, which is excellent in the effect of imparting water repellency to the glass surface and excellent in water repellency.

When the water repellent for glass of the present invention is a window washer, the kinematic viscosity at 25 ° C. is preferably 100 cst or less.
When it is 100 cst or less, the water solubility of the window washer is particularly high, the clogging prevention performance is excellent, and the influence on the painted surface of an automobile or the like is remarkably reduced.

Therefore, in the window washer of the present invention, the kinematic viscosity at 25 ° C. of the amino-modified polysiloxane is in order to achieve both water repellency, water repellency persistence, clogging prevention, and reduced effect on the coating surface. 10 to 100 cst is preferable.

The amino-modified polysiloxane used in the present invention preferably has an amino equivalent of 100 to 10,000, more preferably 300 to 5,000.

When it is 100 or more, it is particularly excellent in the effect of imparting water repellency, and when it is 10000 or less, it is particularly excellent in adsorptivity to the glass surface, and is excellent in water solubility and uniform dispersibility in a water repellent, and particularly in oil films. This is because it has the advantage that it is difficult to be formed and has excellent water repellency.

When the water repellent for glass of the present invention is a window washer, the amino equivalent is preferably 1000 or less.
If it is 1000 or less, the water-solubility of the window washer is particularly high, the clogging prevention performance is excellent, and the influence on the painted surface of an automobile or the like is remarkably reduced.

Therefore, in the window washer of the present invention, the amino equivalent of the amino-modified polysiloxane is 100 to 100 in order to achieve both water repellency / water repellency persistence and clogging prevention / reduction in the influence on the painted surface. 1000 is preferable.

The content of the amino-modified polysiloxane in the water repellent for glass of the present invention is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass.

Since it is 0.01% by mass or more, the falling angle of water droplets adhering to the glass is particularly low, the water repellency is excellent, and 10% by mass or less is particularly difficult to form an oil film and has the advantage of excellent water repellency. is there.

[Acid used in the present invention]
Examples of the acid used in the present invention include organic acids, inorganic acids, and mixtures thereof.
Examples of organic acids include formic acid, acetic acid, lactic acid, mono-, di- and tri-chloroacetic acid, mono-, di- and tri-fluoroacetic acid, p-toluenesulfonic acid, benzenesulfonic acid, ethylsulfonic acid, and methylsulfone. Acid, ethylenedisulfonic acid, dodecylsulfonic acid, trifluoromethylsulfonic acid, perfluoroalkylcarboxylic acids, perfluoroalkylsulfonic acids, maleic acid, picric acid, trihydroxybenzoic acid, trinitrophenol, sulfamic acid, fluorosilicic acid, Examples include chlorosulfonic acid, fluorosulfonic acid, citric acid, malic acid, and mixtures thereof.

Inorganic acids include sulfuric acid, sulfurous acid, fuming sulfuric acid (oleum), hydrofluoric acid, hydrochloric acid, hydrobromic acid, phosphoric acid, phosphorous acid, pyrophosphoric acid, nitric acid, hydrogen sulfide, iodic acid, and mixtures thereof. Is mentioned.

In the present invention, even if it is not a strong acid such as sulfuric acid or sulfonic acid, a carboxylic acid is sufficient, so that a water repellent with higher safety can be obtained. Examples of the carboxylic acid include formic acid, acetic acid, lactic acid, tri-fluoroacetic acid, perfluoroalkylcarboxylic acids, maleic acid, picric acid, and trihydroxybenzoic acid, but have high water repellency. Formic acid, acetic acid and lactic acid are preferred, and formic acid is more preferred.

In addition, the said acid can use the thing of the form of aqueous solution or an alcohol solution, for example, things, such as 10-90% aqueous solution, can be used.

The content of the acid in the water repellent for glass of the present invention is preferably, for example, 0.0001 to 1% by mass, more preferably, as the amount of the “acid” per se when the total water repellent is 100. Is 0.0004-0.5 mass%.

This is because when the amount of the acid is 0.0001% by mass or more, it reacts with the amino-modified polysiloxane to increase its water solubility and is excellent in the effect of preventing clogging of the nozzle of the wind washer. Moreover, it is because it has the advantage that it is excellent in the initial stage water repellency immediately after application | coating of the water repellent to a glass surface, and it is excellent also in the durability of water repellency, when the quantity of an acid is 1 mass% or less.

In addition, it is preferable that the neutralization rate of the water repellent for glass of this invention is 50 to 110%, Most preferably, it is 70 to 80%.
This is because the neutralization rate is 50% or more, the stability in water is high, and the glass is strongly adsorbed, so that high water repellency can be imparted to the glass surface, and the water repellency is also long-lasting.

The neutralization rate refers to a molar conversion ratio of the amount of acid necessary to neutralize the amine value of the entire composition.

[Active agent used in the present invention]
The activator used in the present invention includes alkyl ether sulfate, alkyl sulfate, alkyl sulfonate, alkyl sulfosuccinate, alkyl ether type non-ion, alkyl ester type non-ion, sucrose ester, glycerin ester, alkyl glucoside, amine oxide, and ninol. Nonionic, betaine-type amphoteric, alanine-type amphoteric, imidazoline-type amphoteric, and the like are mentioned, but alkylglucoside is preferred because it hardly damages the painted surface of the vehicle body and the like.

The content of the activator in the water repellent for glass of the present invention is, for example, preferably 0.01 to 2% by mass, and more preferably 0.05 to 1% by mass.

This is because when the amount of the activator is 0.01% by mass or more, the amino-modified polysiloxane is emulsified to enhance its water solubility, and the effect of preventing clogging of the nozzle of the wind washer is excellent. Moreover, it is because the amount of the activator is 2% by mass or less, and it has an advantage of excellent initial water repellency and excellent water repellency immediately after application of the water repellent to the glass surface.

[Aminosilane used in the present invention]
The aminosilane used in the present invention may be any of monoamino, diamino, triamino, and tetraamino. However, as the water repellent, since it is preferable that the hydrophilicity is low, monoamino, diamino, and triamino are preferable. Preferably, it is monoamino or diamino.

Aminosilane has two reactive functional groups and three reactive functional groups, but it has two reactive functional groups because it has a smooth water-repellent surface and a high water-repellent effect imparted to the glass surface. Is preferred.
Examples of the reactive functional group include alkoxy groups such as a methoxy group, an ethoxy group, and a propoxy group, among which a methoxy group or an ethoxy group is preferable, and a methoxy group is particularly preferable.

Accordingly, the aminosilane used in the present invention is most preferably diaminosilane having two reactive functional groups.

Examples of the aminosilane used in the present invention include those having the following structural formulas (specifically, those described in Table 3) described in JP-A-7-41757, but are not limited thereto. In addition, two or more aminosilanes can be used in combination.

Specifically, the following can be obtained from the market.

In the formula [1], R ¹ and R ² are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and among these, a representative of a monovalent hydrocarbon group For example,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, heptyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosyl group; cyclopentyl group, cyclohexyl group, etc. A cycloalkyl group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; an aralkyl group such as a benzyl group and a phenylethyl group; and at least a part of the hydrogen atoms of these groups are halogen atoms; A group substituted with a cyano group, for example, a halogenated hydrocarbon group such as a chloromethyl group, a trifluoropropyl group, a γ-perfluoroalkylpropyl group, a chlorophenyl group, or a cyanoalkyl group such as a cyanoethyl group;
Can be mentioned.
A generally preferred group is a methyl group.

In the present invention, hydrogen atoms are particularly preferable as R ¹ and R ² .

R ³ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms, and typical examples thereof include an alkylene group, an arylene group, and an alkenylene group, preferably a methylene group. , A dimethylene group, a trimethylene group, and a tetramethylene group, among which a trimethylene group is preferable.

R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and specific examples thereof include the same groups as those exemplified for R ¹ and R ² above. Preferred are an alkyl group such as a methyl group and a phenyl group.

X is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms. Among these, typical examples of the monovalent hydrocarbon group are those exemplified for R ¹ and R ² above. The same group can be mentioned. Particularly preferred X in the present invention is a lower alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group.

Moreover, in Formula [1], a is an integer of 0-5, b is an integer of 0-2. As can be understood from the values of a and b, R ² and R ⁴ are not necessarily present.

In the present invention, suitable examples of such aminoalkyl group-containing silanes include, but are not limited to, the following formulas [4] to [19].

The aminosilane used in the present invention preferably has a kinematic viscosity at 25 ° C. of 0.5 to 10 cst, more preferably 1 to 5 cst.

This is because when it is 0.5 cst or more, it is particularly excellent in the effect of imparting water repellency, and when it is 10 cst or less, it is particularly difficult to form an oil film and has the advantage of excellent water repellency.

When the water repellent for glass of the present invention is a window washer, the kinematic viscosity at 25 ° C. is preferably 5 cst or less.
If it is 5 cst or less, the water-solubility of the window washer is particularly high, the clogging prevention performance is excellent, and the influence on the painted surface of an automobile or the like is remarkably reduced.

Therefore, in the window washer of the present invention, in order to achieve both water repellency, water repellency persistence, clogging prevention property, and reduction in the influence on the painted surface, the kinematic viscosity of aminosilane at 25 ° C. is 0. It is preferably 5 to 5 cst.

The aminosilane used in the present invention preferably has an amino equivalent of 50 to 250, more preferably 80 to 220.

When it is 50 or more, it is particularly excellent in the effect of imparting water repellency, and when it is 250 or less, it is particularly excellent in adsorptivity to the glass surface, and it is excellent in water solubility and uniform dispersibility in the water repellent, and particularly in oil films. This is because it has the advantage that it is difficult to be formed and has excellent water repellency.

If the amino equivalent is 250 or less, the water-repellent agent for glass of the present invention has a particularly high water-solubility when the glass washer is a window washer, and has excellent clogging prevention performance, such as an automobile. The effect on the painted surface is significantly reduced.

Therefore, when the amino equivalent of the aminosilane is in the range of 50 to 250, when the glass water repellent of the present invention is a window washer, the water repellency / water repellency persistence and the anti-clogging / coating surface are improved. It is also possible to achieve both reductions in impact.

The content of aminosilane in the water repellent for glass of the present invention is preferably 0.01 to 1% by mass, and more preferably 0.05 to 0.5% by mass.
This is because 0.01% by mass or more has particularly excellent water repellency, and 1% by mass or less has an advantage of being particularly difficult to form an oil film and excellent in water repellency.

In the water repellent for glass of the present invention, the content ratio of amino-modified polysiloxane and aminosilane is preferably 1: 2 to 10: 1, and particularly preferably 1: 1.5 to 5: 1. .

This is because when the ratio of the amino-modified polysiloxane is higher than 1: 2, moderate water repellency is obtained, and when it is less than 10: 1, the durability of water repellency is excellent.

[Water-soluble solvent used in the present invention]
Examples of the water-soluble solvent used in the present invention include glycerin, ethylene glycol, propylene glycol, reduced sucrose, sorbitol, sorbitan, pentaerythritol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monomethyl ether, diethylene glycol and the like. However, glycerin is preferable because it is inexpensive and has excellent paint protection properties.

This water-soluble solvent is used when the water repellent for glass is a wind washer loaded on the body of an automobile. The environment changes from below zero to close to 60 ° C.) The wind washer is altered and the nozzle is clogged, or the alcohol is contained in the wind washer. This has the effect of greatly improving the risk that the color of the paint will be altered due to the difference in the refractive index of light, etc.

[Other components that can be used in the present invention]
In addition to the above, the water repellent for glass of the present invention may contain various solvents such as water and alcohol, and other components generally used in glass repellents, as long as the object of the present invention is not impaired. it can.

For example, various surfactants such as anionic surfactants, amphoteric surfactants, nonionic surfactants, colorants such as stickers, oils, dyes, resins, pigments, fragrances, preservatives, antibacterial agents, Components such as an antioxidant, a chelating agent, a pearling agent, a neutralizing agent, and a pH adjusting agent can be appropriately blended.

Alcohol solvents include methyl alcohol, ethyl alcohol, vinyl (ethenyl) alcohol, acetyl alcohol, propyl alcohol, isopropyl alcohol, propadienyl alcohol, propynyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol Methyl alcohol and the like are preferable.

The alcohol solvent has the effect of preventing freezing, precipitation, and cloudiness of the water repellent for glass by increasing the solubility of the solute.

Although content of the alcohol solvent in the water repellent for glass of this invention is not specifically limited, For example, it can be set as 5-50 mass%.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these.

Prior to the examples, test methods for confirming the performance of the present invention will be described below.

[Testing method for confirming water repellency and water repellency]
After spraying each water repellent of Examples and Comparative Examples with a pump-type hand spray on a glass plate that has been made wet with water by removing oil and dirt on the surface with Compound 99 for glass manufactured by Soft99 The glass surface was rubbed 5 times in a fixed direction with a draining wiper to completely remove the water on the surface, and this was used as a test plate.
After measuring the contact angle (initial water repellency) of this test plate, it was washed with running water for 5 minutes and the contact angle was measured again.

The contact angle was measured using a dynamic contact angle meter FTA125 manufactured by FTA.
The volume of water droplets dropped to measure the contact angle was 4 μl.

It shows that it is excellent in water repellency, so that a contact angle is large.
Moreover, it shows that it is excellent in water-repellent sustainability, so that the maintenance property of this angle is excellent.

[Practical test method for water repellency]
The car windshield (2007 Toyota Motor Corolla Filter, tilt angle of about 40 degrees) was polished with Soft 99 glass compound Z to remove oil and dirt on the surface, making it wet. .
After spraying the water repellents of Examples and Comparative Examples over the entire glass with a hand sprayer, the wiper was operated 45 times (for 1 minute) with LOW while applying water, and then traveled in the rain. .

(Evaluation criteria)
The above practical test results were evaluated according to the following criteria.

If the raindrops on the glass surface move toward the roof at a speed of less than 70 km / h and a good field of view is obtained without a wiper: ○
If there is no wiper and some water droplets remain, but the vehicle was able to run sufficiently: △
If raindrops remain on the glass surface and good visibility cannot be obtained without a wiper, it is difficult to run: ×

[Effect test on painted surface]
Pipet 0.3 ml of each solution of the examples and comparative examples onto the baked painted plate of amino alkyd specified in JIS K2236, leave it in a thermostatic bath at 50 ° C for 8 hours, wash with water, and visually observe the state of the painted surface did.

(Evaluation criteria)
The above practical test results were evaluated according to the following criteria.
No abnormality: ○
Some spots are seen:
There are considerable spots: ×

[Examples 1-5, Comparative Example 1]
Water repellents for glass of Examples 1 to 5 and Comparative Example 1 were produced with the compositions shown in Table 4 below.

[Test Example 1]
According to the water repellency confirmation test method, the initial water repellency (initial contact angle) of Examples and Comparative Examples was confirmed, and the results are shown in Table 5 and FIG.

[Test Example 2]
According to the water repellency persistence confirmation test method, the repellency of the water repellency (maintenance of contact angle) was confirmed in Examples and Comparative Examples, and the results are shown in Table 5 and FIG.

[Test Example 3]
Table 5 shows the results of carrying out a running test using an automobile in accordance with the above-described practical test method for water repellency and evaluating it based on the above evaluation criteria.

[Test Example 4]
Table 5 shows the results of evaluation of Examples and Comparative Examples based on the above evaluation criteria in accordance with the test method for the effect on the painted surface.

[Results of Test Examples 1 and 2]
As can be seen from Table 5 and FIG. 1, as a result of the examination by Test Examples 1 and 2, the water repellents of Examples 1 and 2 have both initial water repellency and water repellent durability compared to those of Comparative Example 1. Was very good.
In Example 3, the initial water repellency was almost the same as that of Comparative Example 1, but as shown in Test Example 2, the water repellency persisted much better than Comparative Example 1.
Examples 4 and 5 were superior to Comparative Example 1 in terms of both initial water repellency and durability, although not as much as in Examples 1 and 2.

In addition, Examples 1-4 whose neutralization rate of the water-repellent agent for glass is 50% or more were excellent in water repellency and its sustainability rather than Example 5.

[Results of Test Example 3]
As can be seen from Table 5, as a result of the running test according to Test Example 3, particularly good results were obtained in Examples 1 and 2.
Also, Examples 3, 4 and 5 were good results, although not as much as Examples 1 and 2.
On the other hand, in Comparative Example 1, traveling was difficult.

[Results of Test Example 4]
As can be seen from Table 5, as a result of the examination by Test Example 4, Example 1 and Example 3 and 4 having the same composition as Example 2 and other Examples 3 and 4 were used in the initial stage except that they were used in combination with a water-soluble solvent. The water repellency and (initial contact angle) and water repellency persistence (maintenance of the contact angle after washing with water) were slightly inferior to those of Example 2, but were excellent in that they could also exhibit the effect of preventing paint stains. .

[Summary of test results]
As can be seen from the results of each of the above test examples and the like, the water repellent for glass surface of the present invention of the example was superior in water repellency and its durability compared to the comparative example. In particular, Comparative Example 1 was superior in water repellency after wetting with water as compared with the water repellency rapidly deteriorating after wetting with water.

It was found that the glass water repellents of the examples were not clogged with the window washer nozzle even after being placed in an automobile internal environment that changed from below zero to nearly 60 ° C.

[Other embodiments]
In addition, when the amino-modified polysiloxane used in the above-mentioned examples was changed to the other ones shown in Tables 1 and 2, good results were obtained as compared with the comparative examples.
Among them, L650, L656, WR1300, WR1600, KF-393, KF-859, KF-880, KF-8004, BY16-209, X-21-161, which are amino-modified polysiloxanes having a kinematic viscosity of 20 to 1000 cst. -A, KF-8008, KF-8012 or amino equivalent is 300 to 5000, L650, L656, WR1300, WR1600, KF-393, KF-861, KF-859, KF-880, KF When -8004, X-21-161-A, KF-8012, SF8417, BY16-209, BY16-849 were used, the water repellency imparting effect and water repellency persistence were particularly good.

In addition, when the aminosilane used in the above examples was changed to the formulas [4] to [19] or other ones described in Table 3, good results were obtained as compared with the comparative example. Among them, the reactive functional group having two aminosilanes (formulas [5], [8], [10], [14], [15], [16], [18]) creates a smooth water-repellent surface, The water repellent effect imparted to the glass surface was excellent, and in particular, diaminosilanes having two reactive functional groups (formulas [5], [14] and [15]) were good.

The water repellent for glass of the present invention is a water repellent for glass that maintains water repellency not only after initial application but also after rain.

It is the figure which graphed the contact angle before and behind water washing of Table 5.

Claims (8)

Amino-modified polysiloxane, acid, and in the water repellent agent containing an active agent, further seen containing an aminosilane and a water-soluble solvent, the content of the amino-modified polysiloxane 0.01 mass% or more, the amount of the aminosilane 0. A water repellent for glass, characterized in that the content ratio of the amino-modified polysiloxane and aminosilane is 01 to 10% by mass or more and 3:10 to 30: 1 . Amino-modified polysiloxane, characterized that, glass water repellent agent according to claim 1 Symbol placement that nature are those having the following (A) and / or (B).
(A) The kinematic viscosity at 25 ° C. is 10 to 5000 cst.
(B) Amino equivalent is 100-15000. Aminosilane, in addition to an amino group, and wherein the one having 2 to 3 reactive functional groups, for glass water repellent agent according to claim 1 or 2. The content of amino-modified polysiloxane is 0.01 to 10.0% by mass, and the content of aminosilane is 0.01 to 1% by mass, according to any one of claims 1 to 3 . Water repellent for glass. The water repellent for glass according to any one of claims 1 to 4 , wherein the content ratio of the amino-modified polysiloxane and the aminosilane is 1: 2 to 10: 1. The water repellent for glass according to any one of claims 1 to 5 , wherein a neutralization rate is 50 to 110%. The water repellent for glass according to any one of claims 1 to 6 , wherein the aminosilane contains one represented by the following formula [1].

(In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms;
R ³ is an unsubstituted or substituted divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
X is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms,
a is an integer of 0 to 5;
b is an integer of 0-2. ) A window washer comprising the water repellent for glass according to any one of claims 1 to 7 .